JPS60151400A - Papermaking additives - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention is a copolymer of acrylamide and/or methacrylamide and a water-soluble unsaturated dibasic acid copolymerizable with these (hereinafter abbreviated as an acrylamide copolymer). A so-called Mannich reaction product of an acrylamide copolymer, which is obtained by reacting formaldehyde and amines with formaldehyde and amines, is used as a papermaking additive.

In recent years, new synthetic organic polymer electrolytes have improved in quality china clay (performance benefits) and economy (cost benefits).
From this point of view, it has been widely used in the paper manufacturing industry, and one of its representative polymers is the Mannich reaction product of polyacrylamide.

In addition, in the production of paper and paperboard, it can be used to improve the water resistance on wire or in presses, or to improve the water resistance of fine fibers,
Improving the yield of fillers, sizing agents, paper strength agents, etc. is extremely meaningful for improving paper quality and improving economic efficiency.For these purposes, polyethyleneimine resins, polyamide resins, Hoffmann reaction products of polyacrylamide, copolymers of (meth)acrylamide and cationic monomers, and Mannich reaction products of polyacrylamide described above have been used, but among these, Hoffmann reaction products of polyacrylamide are The drawback is that the cationic property of the compound decreases, and the efficacy decreases accordingly.In addition, the cationic monomer is expensive, so it is not economically viable to use a co-produced compound of (meth)acrylamide and a cationic monomer. This is disadvantageous, and there is a risk that it is difficult to obtain sufficient effects with polyethyleneimine resins and polyamide resins, probably because they both have low molecular weights.

On the other hand, in the case of the Mannich reaction product of glycoacrylamide described above, it can be said that it is economically advantageous because the amines and formalin for imparting cationic properties to the resin are inexpensive.

Therefore, if the quality, performance, and effectiveness of conventional Mannich reactants, which have these advantages, could be improved, their usefulness would further increase.9 Therefore, the present inventors Polyaquamid, which has been used for a long time, and unsaturated dibasic acids that can be copolymerized with polyaquamid,
When a Mannich reaction product of the acrylamide-based copolymer was prepared using an acrylamide-based copolymer containing 20 mol%, preferably 6 to 12 mol%, compared to the conventional Mannich reaction product, 7): J aqueous The present invention has now been completed by obtaining papermaking additives such as fine fibers, fillers, sizing agents, and paper strength agents that are extremely effective in improving yield.

In other words, the present invention aims to obtain a Mannich reaction product of an acrylamide copolymer which is useful as a papermaking additive by adding a water-soluble unsaturated polyester as the main component. The present invention provides a new and useful papermaking additive which comprises the use of a basic acid in 1.

The acrylamide copolymer used in preparing the papermaking additive of the present invention is acrylamide and/or methacrylamide (hereinafter collectively referred to as [
A monomer (referred to as a month) and a water-soluble unsaturated dibase e copolymerizable with these monomers (a) (hereinafter, these are collectively referred to as "monomer (referred to as b month). or other unsaturated monomers (hereinafter collectively referred to as "monomers (C)") that can be copolymerized with each of the monomers ta+ and Kb). It can be obtained by using it as a component of a copolymerized monomer. , refers to those obtained from monomers (01% (b) and]c).

Here, the usage amount of the above monomer %l is 50 to 99 mol %, preferably 60 to 9 mol %, based on the total monomers.
A range of 7 mol% is suitable; on the other hand, the above monomer f
Similarly, the amount of bl used is 1 based on the total monomer.
~20 mol%, preferably tL< is within the range of 6 to 12 mol%, and furthermore, in the case of using the above monomer Cc), within the range of 0 to 60 mol% based on the total monomers. It is appropriate to use .

The monomers (bl) include maleic acid, fumaric acid, itaconic acid, citraconic acid, their anhydrides, alkali metal salts or ammonium salts, or hydrolyzed water-soluble These include esters that can become unsaturated dibasic acids, but these
Of course, scales can be used with seeds or with two or more types.

Typical examples of the monomer (C) include nonionic vinyl monomers such as styrene, (meth)acrylonitrile, methyl (meth)acrylate, and butyl (meth)acrylate; dimethylamino Propyl (meth)
Vinyl monomers having a tertiary amino group such as acrylamide, diethylamine propyl (meth)acrylamide,
Alternatively, it contains a hydrochloric acid, sulfuric acid or acetate salt of the tertiary amino group-containing vinyl monomer, or a quaternary ammonium salt obtained by reacting the salt with a so-called quaternizing agent such as methyl chloride, dimethyl sulfuric acid or epichlorohydrin. Cationic vinyl monomers such as vinyl monomers;
and unsaturated substances such as (meth)acrylic acid and crotonic acid.
These include basic acids or anionic vinyl heavy bodies such as alkali gold wire salts or ammonium salts of the unsaturated basic acids, and these may be used singly or in combination of two or more.

Next, typical amines used in the Mannich reaction include aliphatic secondary amines such as dimethylamine and diethylamine, but there is no problem in using known and commonly used primary amines in combination.

The Mannich modification rate based on the Mannich reaction is preferably 50 to 100 mol%, preferably 70 mol% or more, and thus has a good storage stability s d'' aqueous property improvement effect and yield 9 improvement effect. A papermaking additive is provided.

Here, the Mannich modification rate refers to the molar percentage of formaldehyde and amines used with respect to the amide group in the acrylamide copolymer described above.

Of course, when carrying out the Mannich reaction, there is no problem in adding either formaldehyde or amines in excess within a range that does not impair storage stability or economic efficiency.

Since the Mannich reaction can be carried out according to a publicly known and commonly used method, the following examples are referred to as representative examples of the present invention, but the present invention is by no means limited to these examples.

In the following, % means 1- unless otherwise specified.
All terms are expressed in weight percent.

Example 1 In a 10DQml four-way flask equipped with a stirrer, a l1fJ'L meter, a reflux condenser tube, and a nitrogen gas introduction tube, 30
9.80% of maleic acid in water, 137.9i of 50% acrylamide in water, 10.84g of Inglovir alcohol and 405.39g of water. ! i' was sampled and prepared, and then the pH was adjusted to 4.5% with 30% sodium hydroxide.
After adjusting the temperature to 5, the temperature of the reaction solution was raised to 65° C. while nitrogen gas was passed through the system to drive out oxygen.

Next, while stirring was continued, 2.28 fl of a 5% ammonium persulfate aqueous solution as a polymerization initiator was added to advance the polymerization reaction, and 1 hour and 2 hours later, while maintaining the same temperature, 1. Added 14g each.

After 5 hours from the start of polymerization, the non-volatile content (NY) was 1
6.0%, the Prutsk field viscosity (hereinafter abbreviated as viscosity) at 25°C is 4.6 []0 cps,
A stable acrylamide copolymer water bath solution having a pH of 467 was obtained.

After that, this polymer water bath solution was cooled to 40°C.
While continuing stirring, add 50% dimethylamine water bath solution σ) 8
Add 7.30 g and 65 g of 57% formalin 7B, then add 5.29 g of 60% sodium hydroxide aqueous solution to adjust the pH to 10, and then adjust the pH to 10.
When kept at ℃ for 2 hours, the viscosity was 6.10 at NV or 15.2%.
A stable Mannich reaction product with a pH of 10.2 was obtained at 0cp8. Hereinafter, this will be referred to as a papermaking additive (A-1).
It is abbreviated as

Examples 2 to 16 and Comparative Examples 1 to 4 The acrylamide thread (co)polymer was prepared in the same manner as in Example 1 by changing the amount of each raw material component used as shown in Table 1. A co)polymer Mannich reaction product was obtained.

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The amount of the aqueous solution is not shown in the table, but it is changed each time.

The properties of the (co)N combinations obtained in each of the above Examples and Comparative Examples are summarized below.

/ Application Examples 1 to 16 and Comparative Application Examples 1 to 41I1 Canadian Standard Freeness (hereinafter abbreviated as C9S, F) obtained from JtJ waste paper was 164 m1
A 0.3 concentration slurry of beaten pulp is added with sulfuric acid
A7!2(SO4)3.14H,O) to pulp at 0.
5% (based on dry @ quantity.

The same applies below), and the pH of this pulp slurry was adjusted to 6.0 using 15% sulfuric acid or 60% sodium hydroxide aqueous solution, and then Examples 1 to 1
The papermaking additives obtained in Comparative Examples 1 to 6 and Comparative Examples 1 to 4 were each added at a concentration of 0.02% based on the pulp, and stirred for 1 minute.

A portion of the pulp slurry thus obtained was separated, one was used for measuring COS, F, to compare the water effect, and the other was used to compare the yield effect of separately separated fine fibers. In order to do so, Tappi Volume 56, No. 10 (19
[Dynamic
Dynamic Drainag
The e-Jar was used for measurement, and the suspension contained in a certain amount of e-liquid obtained by the one-pass test was weighed.

Hereinafter, this weighted value will be expressed as S, S, and murmur.

Application Examples 14 to 26 and Comparative Application Examples 5 to 8 Except that the sulfuric acid sodium chloride was adjusted to 1.5% based on the pulp, and the pH of the pulp slurry was adjusted to 4.5.
In the same manner as Application Examples 1 to 15 and Comparative Application Examples 1 to 4,
The c, s, t'-1 and S, S, l directions were measured.

The results of each of the above application examples and comparative application examples are summarized in Table 2.

Application Examples 27 to 39 and Comparative Application Examples 9 to 1 C, S, and F obtained from 2-column waste paper with a concentration of 1.3% and a pH of 15 were added to a pulp slurry beaten to 393 ILt. 0.07% of the alkyl ketene dimer emulsion based on the pulp was added as a sizing agent, stirred for 2 minutes, and then each of the papermaking additives obtained in Examples 1 to 13 and Comparative Examples 1 to 4 was 0.05% in pulp
After adding the mixture and stirring for another minute, a portion of the thus obtained pulp slurry was collected, and one was used as Application Examples 1 to 1.
It was used for the measurement of C, S, F, and the measurement of S, S, (Ii) in the same way as in Comparative Application Examples 1 to 4, and the rest was paper-made using a hand-paper machine made by Nople & Wood Co., Ltd. in the United States. Then, it was dried in a drum dryer at 11oC for 1 minute to obtain handmade paper with a basis weight of 85±2.!i'/m''.

Afterwards, JIS P-8122 for various handmade papers
According to "Steckicht size degree" and JIS P-
8112, the specific bursting strength 1 was measured.

Application Examples 40-52 and Comparative Application Examples 16-16 Sulfuric acid is added to pulp slurry that has been beaten to a concentration of 6.0% and a pH of 65 and C, S, and F to 393d. Add the clay to a ratio of 0.5% to the pulp, stir for 2 minutes at fw, then dilute 10 times with dilution water whose pH has been adjusted to 6.5, and then use it as a sizing agent. 0.05% of alkenylsuccinic acid pyrohydrate emulsified with cationized starch was added to the pulp and stirred for 2 minutes, followed by each papermaking additive obtained in Examples 1 to 13 and Comparative Examples 1 to 4. Application Example 2
Oki 1 with C, S, F, values similar to 7-39 and 9-12
Measurement of , S, S, value, "Steckicht sizing degree" and "specific bursting strength" were carried out.

Application Examples 56 to 65 and Comparative Application Examples 17 to 20 D degree obtained from used corrugated paper is 6.0% and pH is 4.5
Become. C, S, F, were beaten to a pulp slurry of 693 d, anionic polyacrylamide as a paper strength agent was added at 0.3% based on the pulp, and the mixture was stirred for 2 minutes. Rosin and emulsion were added to the pulp at 1.5% and 0.1%, respectively, and stirred for 2 minutes.
．． The papermaking additives obtained in Examples 1 to 13 and Comparative Examples 1 to 4 were each added in an amount of 0.05% based on the pulp. After stirring for 1 minute, it was processed in the same manner as Application Examples 1 to 13 and Comparative Application Examples 1 to 4 and 1i1 to measure C, S, F, and s, s, I (al "Stekicht size degree ” and “specific bursting strength” were measured.

The results of Application Examples 27 to 65 and Comparative Application Examples 9 to 20 are summarized in Table 3.

Application examples 66 to 78 and comparative application examples 21 to 24L/N=
4/1 Null B KPf, C, S, F, is 610a
In a slurry of 6% concentration of beaten pulp,
0% heavy calcium carbonate powder was added, then 0.5% cationized starch was added to the pulp, stirred for 2 minutes, and then diluted 10 times with dilution water whose pH had been adjusted to 90 in advance. , and further alkyl ketene dimer.
After adding 0.15% of the emulsion to the pulp and stirring for 2 minutes, 0.025% of each papermaking additive obtained in Examples 1 to 132 and Comparative Examples 1 to 4 was added to the pulp for 1 minute. A portion of each of the thus obtained pulp slurries thus obtained was separated and subjected to the measurement of the S, S, and values described in Application Examples 1 to 16 and Ratio 1 Bite Application Examples 1 to 4, and the remaining Application examples 27 to 69 and comparative application examples 9 to
"Stekicht size degree" as described in 12,
JIS P except for the change to incinerate at 500℃
-8128 was used for the measurement of "ash content".

Application Examples 79 to 91 and Comparative Application Examples 25 to 28 Alkenylsuccinic anhydride emulsified with cationized starch in place of cationized starch <IQeeA9 05% based on pulp and in place of alkylketene dimer emulsion Application Examples 66 to 78 and Comparative Application Example 2, except that the content was changed to o, 15% based on the pulp.
S, S, value, [Steckicht sizing degree] and "ash content" were measured in the same manner as in Nos. 1 to 24.

Application examples 91 to 104 and comparative application examples 29 to 32i,
/N=4/1 becomes KP with two cc, s, F, Ka 31
Add 20% talc based on the pulp to a 3% slurry of 0m beaten pulp at 48 degrees Celsius, then add 1.5% and 05% sulfuric acid emulsion based on the pulp, respectively, and stir for 2 minutes. After that, the papermaking additives obtained in Examples 1 to 16 and Comparative Examples 1 to 4 were diluted 10 times with dilution water whose pH had been adjusted to 5.0 in advance. 0025% respectively, and then application examples 66 to 78 and ratio-11 application example 21
Measurements of S, S, value, [Steckicht size degree 1 and "ash content" were carried out in the same manner as in 24.

The results of Application Examples 66 to 104 and Comparative Application Examples 21 to 62 are summarized in Table 4 of Asahi.

// Procedural amendment (voluntary) February 23, 1980 Commissioner of the Patent Office Kazuo Wakasugi 2 Name of invention Paper-making additive 3 Relationship to the case of the person making the amendment Patent Applicant Address: 103 Nihonbashi, Chuo-ku, Tokyo 3-7-20 Dick Ken Vercules Co., Ltd. Representative: Shigeru Kuni Mura 4 Agent address: 3-7 Nihonbashi, Chuo-ku, Tokyo 103) Company name Dainippon Ink & Chemicals Co., Ltd. "Explanation" column 6 Contents of amendment (1) "Table 1" on page 12 of the specification is corrected as shown in the attached sheet.

(2) The statement on page 13, line 4 of the specification is corrected as follows.

``In the pulp slurry of 0.3z concentration of disintegrated pulp, sulfuric acid chloride (A12(SO4)3 ・j) Above procedure amendment (voluntary) Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office, graduated in April 1980 1 Display of the case 1988 Patent Application No. 4002 2 Title of Invention Additive for Paper Making Dick Bercules Co., Ltd. Representative Kawai - In the "Detailed Description of the Invention" section of the line specification, "The tertiary amine 7 group-containing vinyl monomer Correct.

that's all

Claims (1)

[Claims] In order to obtain a Mannich reaction product of an acrylamide-based copolymer used as an additive for paper manufacturing, a water-soluble unsaturated dibasic acid is used as a copolymerization monomer component of the acrylamide-based copolymer, Additive for paper making.